CN107709496A

CN107709496A - The manufacture method of bonding agent, convered structure and convered structure

Info

Publication number: CN107709496A
Application number: CN201680036924.4A
Authority: CN
Inventors: 藤井绘美; 久保敬次; 内野真由美; 风藤修; 辻嘉久
Original assignee: Kuraray Co Ltd
Current assignee: Kuraray Co Ltd
Priority date: 2015-06-23
Filing date: 2016-06-22
Publication date: 2018-02-16
Anticipated expiration: 2036-06-22
Also published as: KR102457858B1; CN107709496B; WO2016208617A1; JPWO2016208617A1; TW201706381A; KR20180021058A; JP6826530B2; TWI710613B

Abstract

The bonding agent of active energy ray curable; it is the bonding agent for being bonded the film comprising PVA based polymers and diaphragm, and it includes PVA based polymers (A), cationically polymerizable compound (B) and cationic polymerization initiators (C)；Convered structure, it is to possess：The convered structure of film, diaphragm and bond layer comprising PVA based polymers, wherein, bond layer is equipped between the film and diaphragm comprising PVA based polymers, and above-mentioned bonding agent is is solidified to obtain by bond layer；With, the manufacture method of convered structure, after the film comprising PVA based polymers is bonded with diaphragm by above-mentioned bonding agent, irradiation active energy beam so that bond layer solidifies.Thus, it is possible to the manufacture method of high bonding force, the bonding agent that the convered structures such as the polarization plates of excellent water resistance can be obtained in addition, the convered structure obtained using the bonding agent and the convered structure is shown during bonding between the film comprising PVA based polymers and diaphragm is provided.

Description

The manufacture method of bonding agent, convered structure and convered structure

Technical field

The present invention relates to including the film of vinol series polymer (being below sometimes referred to as " polyvinyl alcohol " " PVA ") Shown in bonding with diaphragm high bonding force, be furthermore possible to obtain excellent water resistance convered structure bonding agent, use this The convered structure and the manufacture method of the convered structure that bonding agent obtains.

Background technology

The polarization plates of function with transmission and masking light are liquid together with making the liquid crystal that the polarization state of light changes The basic constituent element of crystal display (LCD).Most polarization plates have is fitted with cellulose triacetate on the surface of polarizing coating (TAC) structure of the diaphragm such as film, as the polarizing coating for forming polarization plates, main flow is to make PVA based polymer film uniaxial tensions And iodine system pigment (I is adsorbed in the stretched film being orientated₃ ^-、I₅ ^-Deng), the dichroism pigment of dichroic organic dye etc.It is such Polarizing coating is generally by by the PVA based polymer film uniaxial tensions containing dichroism pigment in advance or in PVA based polymer films Uniaxial tension while adsorb and dichroism pigment or adsorb dichroism pigment after by PVA based polymer film uniaxial tensions Deng and continuously manufacture.

LCD gradually the mini-plant such as calculator and wrist-watch, notebook computer, liquid crystal display, color liquid crystal projecting apparatus, Used in the wide scopes such as the measuring instrument used in LCD TV, vehicle-mounted navigation system, mobile phone, indoor and outdoor, in recent years, Particularly more strongly required to the thin of polarization plates in the mobile purposes such as small-sized notebook computer, mobile phone using increasing Type.

As one of means for being thinned polarization plates, can enumerate polarizing coating, diaphragm slimming, but if by this The problem of a little films are thinned, then generation reduces as the durability and water resistance of polarization plates.Therefore, in recent years, as diaphragm, Propose and substitute the high TAC film of conventional penetrability and use (methyl) acrylic acid series polymeric compounds film, polyester film, knot containing ester ring type Polymer film of structure etc..

When manufacturing polarization plates using such diaphragm, the bonding agent used in order to Nian Jie with polarizing coating is used as, it is known that Such as cationically polymerizable bonding agent (with reference to patent document 1), bag containing the highly branched chain polyalcohol with more than 10 hydroxyls Containing number-average molecular weight be more than 500 and the radiation-curing composition of the compound containing more than 2 hydroxyls is (with reference to patent text 2) etc. offer.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2008-111105 publications

Patent document 2：Japanese Unexamined Patent Publication 2009-227804 publications.

The content of the invention

The invention problem to be solved

However, the highly branched chain polyalcohol of bonding agent described in patent document 1 due to the dissolubility difference included in monomer, therefore The uniformity of bonding agent deteriorates, so as to be produced in terms of the bonding force between the polarizing coating and diaphragm in polarization plate face uneven It is even, as a result, bonding force is easily reduced.In addition, bonding agent described in patent document 2 there is also polarizing coating and diaphragm it Between bonding force is low, the problem of durability and water resistance of polarization plates reduce.

It is an object of the present invention to provide bonding between the film and diaphragm for including PVA based polymers in polarizing coating etc. In show high bonding force, the bonding agent of the convered structures such as the polarization plates of excellent water resistance can be obtained in addition, using the bonding agent The manufacture method of obtained convered structure and the convered structure.

Means for solving the problems

The result that further investigation is repeated in the present inventor etc. to achieve these goals is found, if in active energy beam PVA based polymers (A), the cation of PVA, the polyvinyl butyral resin of non-acetalation etc is coordinated to gather in the bonding agent of curing type Conjunction property compound (B) and cationic polymerization initiators (C), then can improve the film comprising PVA based polymers being bonded and guarantor Bonding force between cuticula, but also water resistance can be improved, based on these opinions, further study repeatedly so as to complete this Invention.

That is, the present invention relates to：

[1] bonding agent of active energy ray curable, it is for being bonded the viscous of the film comprising PVA based polymers and diaphragm Agent is connect, it includes PVA based polymers (A), cationically polymerizable compound (B) and cationic polymerization initiators (C)；

[2] bonding agent according to above-mentioned [1], it also triggers comprising free-radical polymerised compound (D) and radical polymerization Agent (E)；

[3] bonding agent according to above-mentioned [1] or [2], wherein, at least a portion of cationically polymerizable compound (B) is With cationically polymerizable and with free-radical polymerised compound (BD)；

[4] bonding agent according to any one of above-mentioned [1] ~ [3], wherein, vinol series polymer (A) is by acetalation Vinyl alcohol units containing ratio less than the polyvinyl alcohol that 10 moles of % and saponification degree are 80 moles of below %；

[5] bonding agent according to any one of above-mentioned [1] ~ [3], wherein, vinol series polymer (A) is by acetalation Vinyl alcohol units containing ratio for 10 moles of more than % Pioloform, polyvinyl acetal；

[6] bonding agent according to above-mentioned [5], wherein, Pioloform, polyvinyl acetal is polyvinyl butyral resin；

[7] bonding agent according to any one of above-mentioned [1] ~ [6], wherein, the containing ratio of vinol series polymer (A) is 1 ~ 90 mass %；

[8] convered structure, it is to possess：The convered structure of film, diaphragm and bond layer comprising vinol series polymer, its In, bond layer is equipped between the film and diaphragm comprising vinol series polymer, bond layer be by above-mentioned [1] ~ [7] bonding agent any one of solidifies and obtained；

[9] convered structure according to above-mentioned [8] is comprising the film of vinol series polymer is the film of drawn；

[10] convered structure according to above-mentioned [8] or [9], wherein, above-mentioned drawn film is polarizing coating or phase retardation film；

[11] convered structure according to any one of above-mentioned [8] ~ [10], wherein, diaphragm include tri acetyl cellulose, The polymer of (methyl) acrylic acid series polymeric compounds, polyester or the structure containing ester ring type；

[12] convered structure according to any one of above-mentioned [8] ~ [11] comprising the film of vinol series polymer with The bonding force of diaphragm is more than 6.0N/25mm；

[13] manufacture method of convered structure, by the film comprising vinol series polymer and diaphragm by above-mentioned [1] ~ [7] After bonding agent fitting described in any one, irradiation active energy beam is so that bond layer solidifies.

The effect of invention

According to the present invention it is possible to show high bonding during bonding between the film comprising PVA based polymers and diaphragm is provided Power, can obtain in addition excellent water resistance convered structure bonding agent, the convered structure and the convered structure that are obtained using the bonding agent Manufacture method.

Brief description of the drawings

Fig. 1 is the sectional view for an example for schematically showing the convered structure of the present invention.

Embodiment

Below for the detailed description of the invention.

＜ bonding agents ＞

The bonding agent of the present invention is the active energy ray curable for being bonded the film comprising PVA based polymers and diaphragm Bonding agent, it includes PVA based polymers (A), cationically polymerizable compound (B) and cationic polymerization initiators (C).Here, As active energy beam, for example, electromagnetic waves such as ultraviolet, infrared ray, X ray, gamma-rays and in addition Electron ray, proton radiation, neutron ray etc..Among these, seen from curing rate, the availability of irradiation unit, price etc. Point sets out, preferably ultraviolet or electron ray, more preferably ultraviolet.If active-energy is irradiated to the bonding agent of the present invention Ray, then excite the cationic polymerization initiators (C) wherein included, cationically polymerizable compound (B) is mutual react into OK.During being somebody's turn to do, PVA based polymers (A) can be made together to solidify with cationically polymerizable compound (B) and its polymer, energy Enough form bond layer.It should illustrate, should in order to distinguish the PVA based polymers included in bonding agent and composition in the present invention By bonding agent and the PVA based polymers of the film comprising PVA based polymers being bonded, for convenience, will be included in bonding agent PVA based polymers be referred to as " PVA based polymers (A) ".

[PVA based polymers (A)]

As the PVA based polymers (A) that include in the bonding agent of the present invention, can use by vinyl acetate, vinyl formate, Propionate, vinyl butyrate, pivalic acid vinyl acetate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, benzene One kind or two or more polymerization in the vinyl esters such as vinyl formate, methylvinyl acetate and obtain polyvinylesters and to institute Obtain material obtained from polyvinylesters saponification.Among above-mentioned vinyl esters, easiness from the manufacture of PVA based polymers, obtain The easiness that takes, cost etc. are set out, and preferably have ethylene oxy carbonyl (H in the molecule₂C=CH-O-CO-) compound, more Preferably vinyl acetate.

Above-mentioned polyvinylesters preferably obtains using only one kind or two or more vinyl esters as monomer, more preferably only Obtained using a kind of vinyl esters as monomer, can be 1 but as long as in the range of the effect of the present invention is not damaged significantly Kind or vinyl esters of more than two kinds and the copolymer for the other monomers that can be copolymerized with it.

As the other monomers that can be copolymerized with above-mentioned vinyl esters, for example, ethene, propylene, 1- butylene, different The carbon numbers such as butylene are 2 ~ 30 alpha-olefin；(methyl) acrylic acid or its salt；(methyl) methyl acrylate, (methyl) acrylic acid Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid are different Butyl ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) Octadecyl acrylate etc. (methyl) acrylate；(methyl) acrylamide；N- methyl (methyl) acrylamide, N- ethyls (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) acrylamido Propane sulfonic acid or its salt, (methyl) acrylamido propyl-dimethyl amine or its salt, N- methylols (methyl) acrylamide or its spread out (methyl) acrylamide derivatives such as biology；The N- such as N- vinyl formamides, N- vinyl acetamides, NVP Vinylamide；Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl The vinyl ethers such as base ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers； The vinyl cyanides such as (methyl) acrylonitrile；The vinyl halides such as vinyl chloride, vinylidene chloride, PVF, vinylidene fluoride； The allyl compounds such as allyl acetate, allyl chlorine；Maleic acid or its salt, ester or acid anhydrides；Itaconic acid or its salt, ester or acid anhydrides； The vinyl silyl groups compound such as vinyltrimethoxy silane；Unsaturated sulfonic acid or its salt etc..Above-mentioned polyvinylesters can With with the construction unit from one kind or two or more foregoing other monomers.

Construction unit from above-mentioned other monomers ratio shared in above-mentioned polyvinylesters is based on forming polyethylene The molal quantity meter of the entire infrastructure unit of base ester is preferably 15 moles of below %, is more preferably 10 moles of below %, further preferably For 5 moles of below %.

As above-mentioned PVA based polymers (A) it is preferable to use the material of non-grafted copolymerization, but as long as not damaging significantly In the range of the effect of the evil present invention, PVA based polymers (A) can be changed by the one kind or two or more monomer for being capable of graft copolymerization Property.The graft copolymerization can to polyvinylesters and as obtained from by its saponification PVA based polymers at least one of Carry out.As the above-mentioned monomer for being capable of graft copolymerization, for example, unsaturated carboxylic acid or derivatives thereof；Unsaturated sulfonic acid or Its derivative；Carbon number is 2 ~ 30 alpha-olefin etc..Being derived from polyvinylesters or PVA based polymers being capable of graft copolymerization Monomer molal quantity of the ratio of construction unit based on the entire infrastructure unit for forming polyvinylesters or PVA based polymers it is excellent Elect 5 moles of below % as.

As a preferable example for PVA based polymers (A), can enumerate vinyl alcohol units be free of equivalent to by aldehyde or It is " by the vinyl alcohol units of acetalation " of the construction unit of the acetalations such as its derivative or also low even if containing its containing ratio Material.The containing ratio of the vinyl alcohol units by acetalation in such PVA based polymers (A) is based on forming PVA systems polymerization The molal quantity of the entire infrastructure unit of thing (A) is preferably shorter than 10 moles of %, more preferably less than 5 moles of %, even more preferably below 3 rubbed You are %, most preferably 0 mole of %.It should illustrate, in comprising the PVA based polymers by the vinyl alcohol units of acetalation, usual 2 Vinyl alcohol units and 1 aldehyde or derivatives thereof wait reaction and form 1 ethylidene ether structure, but in this manual, will as 1 Ethylidene ether structure is denoted as being made up of 2 " by the vinyl alcohol units of acetalation " (construction units), above-mentioned " by the second of acetalation to consider The containing ratio of alcohol units " and " molal quantity for forming the entire infrastructure unit of PVA based polymers (A) " etc..

Without " by the vinyl alcohol units of acetalation " or even if containing its containing ratio also low above-mentioned PVA based polymers (A) saponification degree contains cationically polymerizable compound, free-radical polymerised from the dissolubility in bonding agent, particularly bonding agent The viewpoints such as the dissolubility during monomers such as compound in these monomers are set out, and preferably 80 moles of below %, more preferably 65 are rubbed You are below %, more preferably 50 moles of below %, particularly preferably 40 moles of below %.If in addition, PVA based polymers (A) Saponification degree it is too low, then the tendency that the bonding force of the film comprising PVA based polymers and diaphragm reduces be present, therefore PVA systems gather The saponification degree of compound (A) be preferably 10 moles of more than %, more preferably 15 moles of more than %, more preferably 20 moles of more than %, Particularly preferably 25 moles of more than %.It should illustrate, PVA based polymers in this specification (including be PVA based polymers (A) Situation) saponification degree refer to relative to the knot that can be converted into vinyl alcohol units possessed by PVA based polymers by saponification Structure unit (typical case for be vinyl ester units) with for the total molal quantity of vinyl alcohol units, mole of the vinyl alcohol units The shared ratio (mole %) of number.Saponification degree can determine according to JIS K 6726-1994 record.

As another preferable example of PVA based polymers (A), can enumerate comprising equivalent to vinyl alcohol units by aldehyde or The Pioloform, polyvinyl acetal of " by the vinyl alcohol units of acetalation " of the construction unit of the acetalations such as its derivative.As above-mentioned aldehyde, For example, formaldehyde, acetaldehyde, propionic aldehyde, n-butanal, isobutylaldehyde, valeral, hexanal, enanthaldehyde, n-octaldehyde, 2- ethylhexyls aldehyde, Hexamethylene aldehyde, furfural, glyoxal, glutaraldehyde, benzaldehyde, 2- tolyl aldehydes, 3- tolyl aldehydes, 4- tolyl aldehydes, to hydroxyl Benzaldehyde, m-hydroxybenzaldehyde, ethylalbenzene, beta-phenyl propionic aldehyde etc..In addition, the derivative as aldehyde, for example, Acetal (dialkyl acetal etc.), vinyl esters, vinyl ethers, the vinyl halide of aldehyde corresponding to being provided by hydrolysis Deng.The vinyl alcohol units by acetalation comprising Pioloform, polyvinyl acetal can be a kind, can also be two or more.Polyvinyl alcohol contracts Among aldehyde, from viewpoints such as bonding force, availability, preferably vinyl alcohol units are included equivalent to by n-butanal or derivatives thereof Etc. the material (polyvinyl butyral resin) of the vinyl alcohol units by acetalation of the construction unit of acetalation.

Vinyl alcohol units (- CH₂- CH (OH) -) containing shared by the entire infrastructure unit for forming Pioloform, polyvinyl acetal Rate is from the viewpoints such as bonding force, more preferably preferably 5 moles of more than %, more preferably 10 moles of more than %, 20 moles of % More than, furthermore it is preferred that being 50 moles of below %, more preferably 40 moles of below %, more preferably 30 moles of below %.

In addition, contained by the vinyl alcohol units of acetalation are shared in the entire infrastructure unit for forming Pioloform, polyvinyl acetal Rate can be such as 10 moles of more than %, gather from the dissolubility in bonding force, bonding agent, particularly bonding agent containing cation The viewpoints such as the dissolubility during monomers such as conjunction property compound, free-radical polymerised compound in these monomers are set out, and preferably 40 Mole more than %, more preferably 50 moles of more than %, more preferably 60 moles of more than %, furthermore it is preferred that for 90 moles of below %, More preferably 85 moles of below %, more preferably 75 moles of below %.

In addition, vinyl ester units containing ratio shared in the entire infrastructure unit for forming Pioloform, polyvinyl acetal is from bonding The viewpoints such as power are set out, preferably 0.1 mole of more than %, more preferably 0.3 mole of more than %, more preferably 0.5 mole of % with On, furthermore it is preferred that for 30 moles of below %, being more preferably 20 moles of below %, more preferably 10 moles of below %, especially excellent Elect 5 moles of below % as.It should illustrate, as the vinyl ester units, can enumerate to manufacture Pioloform, polyvinyl acetal and use Acetalation before PVA based polymers in the unsaponified vinyl ester units that include etc. as representative examples.

The degree of polymerization of above-mentioned PVA based polymers (A) is not particularly limited, it is contemplated that the viscosity of gained bonding agent and then general The bonding agent be coated on diaphragm etc. it is upper when coating etc., the degree of polymerization of PVA based polymers is preferably 2, less than 000, more excellent Elect less than 1,500, more preferably less than 1,000, particularly preferably less than 500 as.In addition, it is contemplated that in gained convered structure The intensity of bond layer etc., preferably more than 100, more preferably more than 150, more preferably more than 200.It should say Bright, the degree of polymerization of alleged PVA based polymers (including situation for PVA based polymers (A)) refers to according to JIS in this specification The average degree of polymerization of K 6726-1994 record measure.In addition, in the case of Pioloform, polyvinyl acetal, in its manufacture, acetalation The front and rear degree of polymerization does not change generally in itself, therefore before the acetalation that will can be used to manufacture Pioloform, polyvinyl acetal The value of the degree of polymerization of PVA based polymers is considered as the degree of polymerization of gained Pioloform, polyvinyl acetal.

The containing ratio of above-mentioned PVA based polymers (A) in the bonding agent of the present invention is from the viscosity of gained bonding agent and then should The viewpoints such as the coating of bonding agent are set out, and preferably below 90 mass %, are more preferably below 50 mass %, more preferably 20 Below quality %.In addition, the viewpoint such as intensity from the bond layer in gained convered structure, the PVA in bonding agent of the invention The containing ratio of based polymer (A) is preferably more than 1 mass %, more preferably more than 2 mass %, more preferably 3 mass % with On.

[cationically polymerizable compound (B)]

As above-mentioned cationically polymerizable compound (B), it is preferable to use have oxetanyl and/or oxygen in intramolecular The compound of heterocycle propyl.Cationically polymerizable compound (B) can be used alone, can also be applied in combination 2 kinds with On.It should illustrate, if at least a portion in using multi-functional compound as cationically polymerizable compound (B), The effect as crosslinking agent can be then played, so it is preferred that.

As the compound in intramolecular with oxetanyl, for example, have 1 oxa- in intramolecular The compound of cyclobutane base, there is more than 2 compound of oxetanyl etc. in intramolecular.In addition, as in molecule The interior compound with oxirane base, for example, the aliphatic compound in intramolecular with oxirane base Thing, there is ester ring type compound of oxirane base etc. in intramolecular.

As the above-mentioned concrete example in compound of the intramolecular with 1 oxetanyl, 3- ethyls -3- can be enumerated Hydroxymethyl oxetane, (3- ethyl -3- oxetanylmethoxies) methylbenzene, the fluoro- [1- (3- ethyl -3- oxa-s of 4- Cyclobutane ylmethoxy) methyl] benzene, 4- methoxyl groups-[1- (3- ethyl -3- oxetanylmethoxies) methyl] benzene, (3- second Base -3- oxetanylmethyls) phenyl ether, (3- ethyl -3- oxetanylmethyls) phenyl ether, [1- (3- ethyls -3- Oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3- ethyl -3- oxetanylmethyls) ether, different ice Chip base epoxide ethyl (3- ethyl -3- oxetanylmethyls) ether, isobornyl (3- ethyl -3- oxetanylmethyls) Ether, 2- ethylhexyls (3- ethyl -3- oxetanylmethyls) ether, ethyl diethylene glycol (3- ethyl -3- oxetanyls Methyl) ether, tetrahydrofurfuryl (3- ethyl -3- oxetanylmethyls) ether, tetrabromo phenyl (3- ethyl -3- oxetanyls Methyl) ether, 2- tetrabromos Phenoxyethyl (3- ethyl -3- oxetanylmethyls) ether, tribromo phenyl (3- ethyl -3- oxa-s Cyclobutane ylmethyl) ether, 2- tribromophenoxies ethyl (3- ethyl -3- oxetanylmethyls) ether, 2- hydroxyethyls (3- second Base -3- oxetanylmethyls) ether, 2- hydroxypropyls (3- ethyl -3- oxetanylmethyls) ether, butoxyethyl group (3- ethyl -3- oxetanylmethyls) ether, five chlorophenyl (3- ethyl -3- oxetanylmethyls) ether, penta-bromophenyl (3- ethyl -3- oxetanylmethyls) ether, bornyl (3- ethyl -3- oxetanylmethyls) ether etc..

As the commercially available product of the above-mentioned compound in intramolecular with 1 oxetanyl, can enumerate OXT-101, OXT-211, OXT-212 (synthesize make for East Asia above) etc..

As the above-mentioned concrete example in compound of the intramolecular with the oxetanyl of more than 2,3 can be enumerated, Double (3- the oxetanyls) -5- oxa-s-nonanes of 7-, 3,3'- (1,3- (2- methenes base) glyceryl is double (epoxide methylene)) be double - Double [(3- ethyl -3- oxetanylmethoxies) methyl] benzene of (3- Ethyloxetanes), 1,4-, double [(the 3- second of 1,2- Base -3- oxetanylmethoxies) methyl] ethane, double [(3- ethyl -3- oxetanylmethoxies) methyl] third of 1,3- Double (3- ethyl -3- oxetanylmethyls) ethers of alkane, ethylene glycol, the double (3- ethyl -3- oxetanyl first of double cyclopentenyl Base) ether, double (3- ethyl -3- oxetanylmethyls) ether of triethylene glycol, the double (3- ethyl -3- oxetanes of tetraethylene glycol Ylmethyl) ether, three ring last of the ten Heavenly stems diyl dimethylenes (3- ethyl -3- oxetanylmethyls) ether, the double (3- ethyl -3- oxygen of 1,4- Azetidine ylmethoxy) butane, double (3- ethyl -3- oxetanylmethoxies) hexanes of 1,6-, double (the 3- second of polyethylene glycol Base -3- oxetanylmethyls) ether, oxirane (EO) modified bisphenol A be double (3- ethyl -3- oxetanylmethyls) Double (3- ethyl -3- oxetanylmethyls) ethers of ether, expoxy propane (PO) modified bisphenol A, the double (3- of the modified hydrogenated bisphenol-As of EO Ethyl -3- oxetanylmethyls) ether, PO modified hydrogenated bisphenol-As double (3- ethyl -3- oxetanylmethyls) ether, EO Modified bisphenol F (3- ethyl -3- oxetanylmethyls) ether etc..

As above-mentioned in commercially available product of the intramolecular with the oxetanyl of more than 2, can enumerate OXT-121, OXT-221 (synthesize make for East Asia above) etc..

As the concrete example conduct of the above-mentioned aliphatic compound in intramolecular with oxirane base, example can be enumerated Such as 1,4- butanediol diglycidyl ethers, 1,6-HD diglycidyl ether, neopentyl glycol diglycidyl ether, three Hydroxymethyl-propane triglycidyl group ether, polyethylene glycol diglycidyl base ether, glycerine triglycidyl group ether, polypropylene glycol Diglycidyl ether class；The alkylene oxide one kind or two or more to the aliphatic polyol addition such as ethylene glycol, propane diols, glycerine The poly epihydric alcohol base ethers of PPG obtained from hydrocarbon；The diglycidyl esters of aliphatic long-chain binary acid；Fat Single glycidyl ethers of fat race higher alcohol；The glycidyl esters of higher fatty acids；Epoxidised soybean oil；Epoxy is stearic Acid butyl ester；Octyl epoxy stearate；Epoxidation linseed oil；Epoxidized polybutadiene etc..

As the commercially available product of the above-mentioned aliphatic compound in intramolecular with oxirane base, SR- can be enumerated NPG, SR-16H, SR-PG, SR-TPG (being above this pharmaceutical industries of slope system)；PG-202, PG-207 (are melted into for Dongdu make above) Deng.

As the concrete example conduct of the above-mentioned ester ring type compound in intramolecular with oxirane base, 3 can be enumerated, 4- 7-oxa-bicyclo[4.1.0 formic acid 3', 4'- epoxycyclohexyl-methyls ester, 2- (3,4- epoxycyclohexyl -5,5- spiral shell -3,4- epoxies) hexamethylene Double (3,4- epoxycyclohexyl-methyls) esters of alkane-trimethylene-formal, adipic acid, the double (3,4- epoxy -6- methyl cyclohexanes of adipic acid Ylmethyl) ester, 3', 4'- epoxy -6'- cyclohexanecarboxylic acid 3,4- epoxy -6- methyl cyclohexanes base ester, 6-caprolactone be modified 3', 4'- 7-oxa-bicyclo[4.1.0 formic acid 3,4- epoxycyclohexyl-methyls ester, trimethyl caprolactone modification 3', 4'- 7-oxa-bicyclo[4.1.0 formic acid 3, 4- epoxycyclohexyl-methyls ester, Beta-methyl-δ-valerolactone are modified 3', 4'- 7-oxa-bicyclo[4.1.0 formic acid 3,4- epoxycyclohexyl-methyls Ester, di-2-ethylhexylphosphine oxide (3,4- 7-oxa-bicyclo[4.1.0s), two (3,4- epoxycyclohexyl-methyls) ethers, ethylenebis (the 3,4- rings of ethylene glycol Oxygen naphthenic acid ester), epoxide ring di-2-ethylhexyl hexahydrophthalate, 2- ethylhexyls of epoxy hexahydrophthalic acid two etc..

As the commercially available product of the above-mentioned ester ring type compound in intramolecular with oxirane base, セロキ can be enumerated サイド2021、セロキサイド2021P、セロキサイド2081、セロキサイド2083、セロキサイド 2085、エポリードGT-300、エポリードGT-301、エポリードGT-302、エポリードGT-400、エポリー De 401, エポリー De 403 (being above Co., Ltd.'s ダイセ Le systems) etc..

The containing ratio of above-mentioned cationically polymerizable compound (B) in the bonding agent of the present invention is without especially system limit, from institute Obtain the viewpoints such as the intensity of bond layer in convered structure to set out, preferably below 98 mass %, be more preferably below 95 mass %, enter One step is preferably below 90 mass %, is particularly preferably below 70 mass %.In addition, from the viscosity of gained bonding agent and then this is viscous Connect the viewpoints such as the coating of agent to set out, the containing ratio of the cationically polymerizable compound (B) in bonding agent of the invention is preferably More than 10 mass %, more preferably more than 20 mass %, more preferably more than 30 mass %.

[cationic polymerization initiators (C)]

As above-mentioned cationic polymerization initiators (C), can use promote bonding agent to be wrapped by irradiating active energy beam The PVA based polymers (A) contained and the compound of the reaction of cationically polymerizable compound (B).As such cationic polymerization Initiator (C), for example, the salt series initiators such as sulfonium salt series initiators, salt compounded of iodine series initiators；Sulfonic acid, carboxylic Esters of gallic acid, aryl diazonium salts, iron-arene complexes, pyridiniujm, quinolinium, the compound etc. of the methyl of nitrobenzene containing O-, it is excellent Elect salt series initiators, more preferably sulfonium salt series initiators, salt compounded of iodine series initiators as.These cationic polymerization initiators (C) It can be used singly or in combination of two or more.

As above-mentioned sulfonium salt series initiators, for example, to phenylphenylmethyl Methylsulfonium Salt, to pheiiyldimetliyl sulfonium The p-hydroxybenzene benzyl Methylsulfonium Salts such as salt, benzyl methyl-p-hydroxybenzene sulfonium hexafluoro antimonate；Triphenyl sulfonium salt, two The triarylsulfonium salts such as phenyl [4- (thiophenyl) phenyl] sulfonium salt；Double [two (beta-hydroxy ethyoxyl) phenyl sulfoniums] the diphenyl sulphur of 4,4'- Double hexafluoro antimonates of ether etc. possess two sulfonium salts of double [4- (diphenyl sulfonium) phenyl] thioether skeletons etc..

As the counter-anion of the sulfonium salt in above-mentioned sulfonium salt series initiators, SbF can be enumerated₆ ^-、AsF₆ ^-、PF₆ ^-、BF₄ ^- Deng, among these, from the viewpoint of reactivity, stability, preferably SbF₆ ^-、PF₆ ^-。

As above-mentioned salt compounded of iodine series initiators, for example, diphenyl iodine, double (4- tert-butyl-phenyls) iodine, Salt compounded of iodine such as (4- tert .- butoxyphenyls) phenyl-iodide, (4- methoxyphenyls) phenyl-iodide etc..

As cationic polymerization initiators (C), from the viewpoint of heat endurance, particularly preferably diphenyl [4- (benzene sulphur Base) phenyl] triarylsulfonium salt such as sulfonium salt.

As above-mentioned cationic polymerization initiators (C) commercially available product, for example, " CPI-100P " (サ Application アプロ System), " CPI-101A " (サ Application アプロ systems), " IRGACURE 250 " (BASF systems), " アデカオプトマー SP-172 " (ADEKA systems), " アデカオプトマー SP-170 " (ADEKA systems), " アデカオプトマー SP-152 " (ADEKA systems), " アデカオプトマー SP-150 " (ADEKA systems), " サ Application エイ De SI-60L " (three new chemical industry systems), " サ Application エイ De SI-80L " (three new chemical industry systems), " サ Application エイ De SI-100L " (three new chemical industry systems), " サ Application エイ De SI-150L " (three new chemical industry systems) etc..

The containing ratio of above-mentioned cationic polymerization initiators (C) in the bonding agent of the present invention is not particularly limited, it is contemplated that Because of the acid from cationic polymerization initiators (C) to the shadow of the film comprising PVA based polymers, diaphragm or bond layer Ring, preferably below 10 mass %, be more preferably below 5 mass %, more preferably below 3 mass %.It is in addition, it is contemplated that viscous Connect agent curing rate and solidification after bonding force etc., cationic polymerization initiators (C's) in bonding agent of the invention contains Rate is preferably more than 0.01 mass %, is more preferably more than 0.05 mass %, more preferably more than 0.1 mass %.

The bonding agent of the present invention preferably also includes free-radical polymerised compound (D) and radical polymerization initiator (E).Such as Fruit irradiates active energy beam to the bonding agent, then excites the cationic polymerization initiators (C) and radical polymerization wherein included Close initiator (E), the mutual reaction of cationically polymerizable compound (B), the mutual reaction of free-radical polymerised compound (D) etc. Carry out.During being somebody's turn to do, PVA based polymers (A) and cationically polymerizable compound (B), free-radical polymerised compound can be made (D) together solidify with their polymer, bond layer can be formed.In addition, at least one in cationically polymerizable compound (B) Part can be with cationically polymerizable and with free-radical polymerised compound (BD).Cationically polymerizable compound (B) when at least a portion in is with cationically polymerizable and with free-radical polymerised compound (BD), preferably also wrap Containing radical polymerization initiator (E).

The bonding agent of the present invention includes cationically polymerizable compound (B), therefore to the viscous of the film comprising PVA based polymers Connecing property is excellent.In addition, if the bonding agent of the present invention also includes free-radical polymerised compound (D), further increase pair The bonding force of diaphragm.As the bonding agent of the present invention, improved from further to the film comprising PVA based polymers and diaphragm From the viewpoint of both bonding forces, preferably together comprising PVA based polymers (A), cationically polymerizable compound (B), sun The bonding agent of cation polymerization initiator (C), free-radical polymerised compound (D) and radical polymerization initiator (E)；Together include PVA based polymers (A), with cationically polymerizable and with free-radical polymerised compound (BD), cationic polymerization trigger Agent (C) and the bonding agent of radical polymerization initiator (E).

[free-radical polymerised compound (D)]

As above-mentioned free-radical polymerised compound (D), it is preferable to use the change in intramolecular with (methyl) acryloyl group Compound.Free-radical polymerised compound (D) can be used singly or in combination of two or more.It should illustrate, if At least a portion in using multi-functional compound as free-radical polymerised compound (D), then can play as friendship Join the effect of agent, so it is preferred that.

As the above-mentioned concrete example in compound of the intramolecular with (methyl) acryloyl group, (methyl) propylene can be enumerated Sour methyl esters, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid are just Butyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid isoamyl Ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (first Base) 2-EHA, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (first Base) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) acrylic acid is hard Fat ester, the different stearyl ester of (methyl) acrylic acid, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) third Olefin(e) acid borneol base ester, (methyl) acrylic acid tricyclodecyl ester, (methyl) acrylic acid Bicvclopentyl ester, (methyl) acrylic acid bicyclic penta Alkenyl epoxide ethyl ester, (methyl) acrylic acid 4- butylcyclohexyls ester, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxyls Base propyl ester, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxyl -3- benzene Epoxide propyl ester, (methyl) acrylate, butoxy ethyl, (methyl) ethioxy binaryglycol ester, (methyl) acrylic acid benzene first Ester, (methyl) acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) Acrylate polyethylene glycol monoester, (first Base) acrylic acid polypropylene glycol monoesters, (methyl) methoxyethyl glycol ester, (methyl) ethoxyethyl acrylate, (first Base) methoxyethyl macrogol ester, (methyl) methoxyethyl polypropylene glycol ester, (methyl) acrylate Ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid 7- amino -3,7- dimethyl monooctyl ester, 4- acryloyl groups Morpholine, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris epoxide ethyl (methyl) acrylate, Ji Wusi Alcohol three (methyl) acrylate, ethylene glycol two (methyl) acrylate, triethylene glycol diacrylate, tetraethylene glycol two (methyl) Acrylate, polyethylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, (first of 1,6-HD two Base) acrylate, neopentyl glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, bisphenol-A 2-glycidyl Double ends (methyl) acrylic acid addition body, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) propylene of base ether Acid esters, polyester two (methyl) acrylate, three (2- hydroxyethyls) isocyanuric acid ester three (methyl) acrylate, three (2- (2,3- Dihydroxy propoxyl group) ethyl) isocyanuric acid ester three (methyl) acrylate, three (2- hydroxyethyls) isocyanuric acid esters two (methyl) Acrylate, cyclohexanedimethanol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, as bis-phenol Two (methyl) acrylate, the oxirane as hydrogenated bisphenol A of the glycol of A oxirane or the addition body of expoxy propane Or two (methyl) acrylate, the diglycidyl ether addition (methyl) to bisphenol-A of the glycol of the addition body of expoxy propane Epoxy obtained from acrylate (methyl) acrylate etc..

In addition, the other examples as above-mentioned free-radical polymerised compound (D), for example, bisphenol type epoxy Acrylate, phenol novolak-type epoxy acrylate, cresol novolak type epoxy acrylate etc. Epoxy (methyl) acrylic ester resin；Carboxy-modified epoxy (methyl) acrylic ester resin；Make by polyalcohol with it is organic different Carbamate (first obtained from carbamate resins and (methyl) acrylate reactions of hydroxyl that cyanate obtains Base) acrylic ester resin；The resin of (methyl) acryloyl group is imported by ester bond in polyalcohol；Polyester (methyl) acrylic acid Ester system resin；(methyl) acrylamide based compounds such as N- hydroxyethyls (methyl) acrylamide etc..

The containing ratio of above-mentioned free-radical polymerised compound (D) in the bonding agent of the present invention is not particularly limited, from institute Obtain the viewpoints such as the intensity of bond layer in convered structure to set out, preferably below 98 mass %, be more preferably below 95 mass %, enter One step is preferably below 90 mass %, is particularly preferably below 70 mass %.In addition, from the viscosity of gained bonding agent and then this is viscous Connect the viewpoints such as the coating of agent to set out, the containing ratio of the free-radical polymerised compound (D) in bonding agent of the invention is preferably More than 10 mass %, more preferably more than 20 mass %, more preferably more than 30 mass %.

[radical polymerization initiator (E)]

As above-mentioned radical polymerization initiator (E), can use can be promoted comprising viscous by irradiating active energy beam Connect the compound of the reaction of the free-radical polymerised compound (D) of agent., can be with as such radical polymerization initiator (E) Enumerate the carbonyls such as acetophenones, benzophenone, Michler's keton class, benzoin class；Tetra methylthiuram list thioether, Sulphur compounds such as thioxanthones etc., preferably carbonyls.These radical polymerization initiators (E) can be used alone, Two or more can be applied in combination.

As above-mentioned acetophenones, for example, 1- hydroxycyclohexylphenylketones, 2,2- dimethoxy -1,2- hexichol Base second -1- ketone, 2- hydroxy-2-methyl -1- phenyl propyl- 1- ketone etc..

As above-mentioned benzophenone, for example, benzophenone, benzoyl benzoic acid, dihydroxy benaophenonel, 3,3'- dimethyl -4- methoxy benzophenones, acrylated benzophenone etc..

As above-mentioned benzoin class, for example, benzoin, benzoin methyl ether, benzoin isopropyl ether etc..

As radical polymerization initiator (E), in reactivity, the transparency etc. more preferably acetophenones or hexichol first Ketone, more preferably 1- hydroxycyclohexylphenylketones.

As above-mentioned radical polymerization initiator (E) commercially available product, for example, " (the 1- hydroxyls of IRGACURE 184 " Cyclohexyl-phenyl ketone；BASF systems), " ソ Le バスロ Application BIPE " (dark fund chemical conversion system), " ソ Le バスロ Application BIBE " (dark funds Into system), the " (2,2- dimethoxy -1,2- diphenyl second -1- ketone of IRGACURE 651 "；BASF systems), the " (2- of DAROCUR 1173 " Hydroxy-2-methyl -1- phenyl propyl- 1- ketone；BASF systems), " IRGACURE 2959 " (BASF systems), the " (BASF of IRGACURE 127 " System), " IRGACURE 907 " (BASF systems), " IRGACURE 369 " (BASF systems), " KAYACURE BP " (Japanese chemical drug system), " IRGACURE 379 " (BASF systems), " DAROCUR TPO " (BASF systems), " IRGACURE 819 " (BASF systems), " IRGACURE 819DW " (BASF systems), " IRGACURE 784 " (BASF systems), " IRGACURE OXE 01 " (BASF systems), " IRGACURE OXE 02 " (BASF systems), " IRGACURE 754 " (BASF systems), " IRGACURE 500 " (BASF systems), " IRGACURE 1800 " (BASF systems), " IRGACURE 1870 " (BASF systems), " DAROCUR 4265 " (BASF systems), " KAYACURE DETX-S " (days This chemical drug system), " ESACURE KIP 150 " (Lamberti systems), " S-121 " (development of シンコー skills), " セイクオー Le BEE " (Seiko chemistry system) etc..

The containing ratio of above-mentioned radical polymerization initiator (E) in the bonding agent of the present invention is not particularly limited, from preventing The viewpoint such as reduction of the low molecule quantization of solidfied material and heat resistance caused by it is set out caused by curing rate is too fast, Preferably below 10 mass %, it is more preferably below 5 mass %, more preferably below 3 mass %.In addition, it is contemplated that bonding agent Curing rate and solidification after bonding force etc., the containing ratio of the radical polymerization initiator (E) in bonding agent of the invention is excellent Elect as more than 0.01 mass %, more preferably more than 0.05 mass %, more preferably more than 0.1 mass %.

[with cationically polymerizable and with free-radical polymerised compound (BD)]

Can be with cationically polymerizable as at least a portion as described previously for cationically polymerizable compound (B) And there is free-radical polymerised compound (BD).If bonding agent is included with cationically polymerizable and with radical polymerization Property compound (BD), then should polymerize with PVA systems with cationically polymerizable and with free-radical polymerised compound (BD) The cross-linking reaction of thing (A), cationically polymerizable compound (B), free-radical polymerised compound (D) etc. is carried out etc., is further carried The intensity of bond layer in high gained convered structure, the result is that further increasing the film comprising PVA based polymers and guarantor The bonding force of cuticula, so it is preferred that., can as this with cationically polymerizable and with free-radical polymerised compound (BD) To be preferably used in intramolecular with oxetanyl and/or oxirane base and also with (methyl) acryloyl group Compound.It can be used alone with cationically polymerizable and with free-radical polymerised compound (BD), can also group Conjunction uses two or more.

As above-mentioned with cationically polymerizable and with the concrete example of free-radical polymerised compound (BD), Ke Yiju Go out (methyl) acrylate of the epoxy radicals containing ester ring type such as (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates；(methyl) acrylic acid (methyl) acrylate of the formulas containing fat chain such as ethylene oxidic ester epoxy radicals；3- ethyls -3- (methyl) acryloyloxymethyl oxa- (methyl) acrylate of the oxygen heterocycle butane group such as cyclobutane etc..

It is above-mentioned with cationically polymerizable and with free-radical polymerised compound (BD) in the bonding agent of the present invention Containing ratio be not particularly limited, from viewpoints such as the intensity of the bond layer in gained convered structure, preferably 90 mass % with Under, more preferably below 85 mass %, more preferably below 80 mass %, particularly preferably below 60 mass %.In addition, from The viewpoint such as the viscosity of gained bonding agent and then the coating of the bonding agent is set out, and has cation in bonding agent of the invention Polymerism and containing ratio with free-radical polymerised compound (BD) are preferably more than 5 mass %, more preferably 10 mass % Above, more preferably more than 15 mass %.

[other optional members]

The bonding agent further can contain except above-mentioned PVA based polymers (A), cationically polymerizable compound (B), cation Polymerization initiator (C), free-radical polymerised compound (D) and radical polymerization initiator (E) (should illustrate, cationic polymerization Property compound (B) include with cationically polymerizable and there is free-radical polymerised compound (BD)) outside its His composition.As the other compositions, for example, crosslinking agent, sensitizer, diluent, tackifier, softening agent, filler, Stabilizer, pigment, dyestuff etc..The other compositions can be organic compound, or inorganic compound.

(crosslinking agent)

Above-mentioned crosslinking agent is by PVA based polymers (A), cationically polymerizable compound (B), free-radical polymerised compound (D) Obtained Deng crosslinking, thus further increase the intensity of the bond layer in gained convered structure, the result is that further improving The bonding force of film and diaphragm comprising PVA based polymers.Above-mentioned crosslinking agent can be used only a kind, can also be applied in combination 2 More than kind.

As above-mentioned crosslinking agent, for example, the nitrogen compounds such as polyoxazoline, methyl diphenylene diisocyanate etc. Titanium sub-group compounds such as the zirconium compounds such as the aldehyde compounds such as isocyanate compound, glutaraldehyde, zirconium carbonate ammonium, lactic acid titanium etc..

The containing ratio of crosslinking agent in the bonding agent of the present invention is not particularly limited, from the viscosity of gained bonding agent and then The viewpoints such as the coating of the bonding agent are set out, the containing ratio of crosslinking agent is preferably below 20 mass %, more preferably 15 mass % with Under.In addition, the containing ratio of crosslinking agent can be for example more than 1 mass %.

(sensitizer)

Above-mentioned sensitizer is by making the sensitivity of active energy beam mobile or extending to promote the solidification of bonding agent.As so Sensitizer, for example, n-butylamine, di-n-butyl amine, tri-n-butyl phosphine, allyl sulfenyl uric acid, triethylamine etc., Preferably triethylamine.

Above-mentioned sensitizer is preferably applied in combination with cationic polymerization initiators (C), radical polymerization initiator (E).Sensitization Agent relative to the quality ratio of cationic polymerization initiators (C) and radical polymerization initiator (E) and the total of sensitizer in order to Fully obtain its effect and preferably more than 5 mass %, more preferably more than 10 mass %.The upper limit of the quality ratio of sensitizer does not have There is special limitation, can be for example below 90 mass %.

(diluent)

Above-mentioned diluent adjusts the viscosity of bonding agent and solidifies the mechanical strength after the bonding agent.As the diluent, Ke Yiju Go out not having the compound of active energy ray-curable group, specifically, for example, phthalate, non- Aromatic diacid ester, aliphatic ester, the ester of PAG, phosphoric acid ester, trimellitic acid esters, chlorinated paraffin, hydrocarbon system Oil, operation oil, polyethers, as polyester plasticizer that 2 yuan of acid and 2 yuan of alcohol obtain, vinyl monomer is polymerize obtained from Vinyl polymers etc..These desactivation compounds can be used singly or in combination of two or more.It should say Bright, diluent can have functional group's (hydroxyl, carboxyl, halogen radical etc.) in addition to active energy ray-curable base.

As above-mentioned phthalate, for example, dibutyl phthalate, dibutyl phthalate (DHP), Phthalic acid two (2- ethylhexyls) ester, phthalic acid butyl benzyl ester etc..

As above-mentioned non-aromatic dibasic acid ester, for example, dioctyl adipate, di-n-octyl sebacate, decanedioic acid two Butyl ester, succinic acid isodecyl ester etc..

As above-mentioned aliphatic ester, for example, butyl oleate, acetyl group methyl ricinolcic acid etc..

As the ester of above-mentioned PAG, for example, diethylene glycol dibenzoate, triethylene glycol hexichol Formic acid esters, pentaerythritol ester etc..

As above-mentioned phosphoric acid ester, for example, tricresyl phosphate, tributyl phosphate etc..

As above-mentioned hydrocarbon system oil, for example, alkyl biphenyl, partially hydrogenated terphenyl etc..

As above-mentioned polyethers, for example, PPG；The hydroxyl of PPG is converted into ester group, ether Derivative etc. obtained from base etc..Here, as PPG, for example, polyethylene glycol, polypropylene glycol, poly- four Asia Methylene glycol etc..

As above-mentioned 2 yuan of acid, for example, decanedioic acid, adipic acid, azelaic acid, phthalic acid etc..As above-mentioned 2 First alcohol, for example, ethylene glycol, diethylene glycol, triethylene glycol, propane diols, DPG etc..

As above-mentioned vinyl polymers, for example, (methyl) acrylic acid series polymeric compounds, polybutene, poly- isobutyl Alkene, styrenic (polystyrene, Poly-alpha-methylstyrene etc.), diene polymer (polybutadiene, polychlorostyrene fourth two Alkene etc.), vinyl ethers based polymer, their copolymer (hycar etc.) etc..

The number-average molecular weight (Mn) of diluent is preferably less than 15,000, is more preferably less than 10,000, further preferably For 8, less than 000, furthermore it is preferred that being more than 400, more preferably more than 800, more preferably 1, more than 000.It is dilute by making The number-average molecular weight (Mn) of agent is released as the viscosity of gained bonding agent below the above-mentioned upper limit, can be made to reach appropriate scope, so as to Improve the treatability of bonding agent.In addition, by making the number-average molecular weight (Mn) of diluent be more than above-mentioned lower limit, can suppress dilute Release agent to flow out with the time from the solidfied material after solidification bonding agent, initial physical property can be maintained for a long time.

Its molecular weight distribution (Mw/Mn) is not particularly limited when diluent is polymer, and usually less than 1.8, preferably 1.7 Below, less than 1.5, more preferably less than 1.3 are more preferably.

The containing ratio of diluent in the bonding agent of the present invention is not particularly limited, the bond layer from gained convered structure The viewpoint such as intensity set out, preferably below 70 mass %, more preferably below 50 mass %, more preferably 30 mass % with Under, can be below 10 mass %.

(tackifier)

Above-mentioned tackifier can assign adhesiveness to the solidfied material after solidification bonding agent.As tackifier, for example, perfume (or spice) Beans ketone indene resin, phenolic resin, p-t-butyl phenol acetylene resin, phenol formaldehyde resin, terpene resin, synthesis terpenes Resin, aromatic-modified terpene resin, xylene formaldehyde resin, aromatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, monoolefine, two The oligomer of alkene, hydrocarbon resin, hydrogenated hydrocarbon resins, polybutene, the polyol ester of rosin, hydrogenated rosin, hydrogenated wood rosin, hydrogenation Rosin and single methanol or the ester of polyalcohol formation, turpentine resin etc..Among these, preferably terpene resin, synthesis terpene resin, Aromatic-modified terpene resin, fatty family saturated oil resin, rosin ester, disproportionated rosin ester, hydrogenated wood rosin glycerol ester, aliphatic through-stone Oleoresin (C5 systems fatty family Petropols, C5C9 systems fatty family Petropols etc.) or modified aliphatic through-stone oil tree Fat.

[manufacture method of bonding agent]

The manufacture method of the bonding agent of the present invention has no particular limits, such as can be by mixing, stirring PVA based polymers (A), cationically polymerizable compound (B), cationic polymerization initiators (C) and according to it is expected addition it is free-radical polymerised Compound (D), radical polymerization initiator (E), other compositions (should illustrate, cationically polymerizable compound (B) includes having Cationically polymerizable and there is free-radical polymerised compound (BD)) etc. it is one kind or two or more among optional member And easily manufacture.

[film for including PVA based polymers]

The bonding agent of the present invention is used to be bonded the film comprising PVA based polymers (sometimes by " film for including PVA based polymers " referred to as For " PVA based polymers film ") and diaphragm.As the PVA based polymers included in PVA based polymer films, can use second Vinyl acetate, vinyl formate, propionate, vinyl butyrate, pivalic acid vinyl acetate, tertiary ethylene carbonate, laurate second One kind or two or more polymerization in the vinyl esters such as alkene ester, stearic acid vinyl ester, vinyl benzoate, methylvinyl acetate and obtain To polyvinylesters and to material obtained from gained polyvinylesters saponification.Among above-mentioned vinyl esters, it polymerize from PVA systems The easiness of the manufacture of thing, the easiness obtained, cost etc. are set out, and preferably have ethylene oxy carbonyl (H in the molecule₂C= CH-O-CO- compound), more preferably vinyl acetate.

As above-mentioned PVA based polymers it is preferable to use the material of non-grafted copolymerization, but as long as not damaging this significantly In the range of The effect of invention, PVA based polymers can be capable of the monomer modified of graft copolymerization by one kind or two or more.This connects Branch copolymerization can to polyvinylesters and as obtained from by its saponification PVA based polymers at least one of carry out.Make For the above-mentioned monomer for being capable of graft copolymerization, for example, unsaturated carboxylic acid or derivatives thereof；Unsaturated sulfonic acid or its derivative Thing；Carbon number is 2 ~ 30 alpha-olefin etc..The monomer for being capable of graft copolymerization is derived from polyvinylesters or PVA based polymers Molal quantity of the ratio of construction unit based on the entire infrastructure unit for forming polyvinylesters or PVA based polymers be preferably 5 Mole below %.

In above-mentioned PVA based polymers, a part of in its hydroxyl can be crosslinked, and can not also be crosslinked.In addition, above-mentioned PVA In based polymer, a part of in its hydroxyl can form ethylidene ether structure with the reaction such as the aldehyde compound such as acetaldehyde, butyraldehyde, also may be used Ethylidene ether structure is not formed not reacted with these compounds.

The degree of polymerization of above-mentioned PVA based polymers is not particularly limited, and preferably 1, more than 000.By making PVA based polymers The degree of polymerization be 1, more than 000, can further improve gained polarizing coating polarization property.If the polymerization of PVA based polymers Height is spent, then the step of when causing the manufacturing cost of PVA based polymers to rise, be film-made be present by the bad tendency of property, therefore The degree of polymerization of PVA based polymers is more preferably in the range of 1,000 ~ 10,000, more preferably 1,500 ~ 8,000 scope It is interior, particularly preferably in the range of 2,000 ~ 5,000.

It is excellent from the viewpoint of the humidity resistance of the saponification degree of above-mentioned PVA based polymers from polarizing coating obtained by making reaches good Elect 95 moles of more than %, more preferably 98 moles of more than %, more preferably 99 moles of more than % as, particularly preferably 99.3 rub You are more than %.

PVA based polymers film can include plasticizer together with above-mentioned PVA based polymers.By making PVA based polymer films Comprising plasticizer, raising of treatability, draftability of PVA based polymer films etc. can be realized.As plasticizer, preferably using more First alcohol, as concrete example, ethylene glycol, glycerine, propane diols, diethylene glycol, two glycerine, triethylene glycol, tetrem can be enumerated Glycol, trimethylolpropane etc., PVA based polymers film can include one kind or two or more in these plasticizer.Among these, From the viewpoint of the draftability for making PVA based polymer films reaches better, preferably glycerine.

The content of plasticizer in PVA based polymer films is preferably 2 ~ 20 mass relative to the mass parts of PVA based polymers 100 Part, more preferably 3 ~ 17 mass parts, more preferably 4 ~ 14 mass parts.By making the plasticizer in PVA based polymer films Content is more than 2 mass parts to improve the draftability of PVA based polymer films relative to the mass parts of PVA based polymers 100.It is another Aspect, by making the content of the plasticizer in PVA based polymer films relative to the mass parts of PVA based polymers 100 be 20 mass parts Hereinafter, plasticizer can be suppressed and ooze out into the surface of PVA based polymer films so as to the treatability reduction of PVA based polymer films.

In addition, using it is aftermentioned be used to manufacture the film stoste of PVA based polymer films to manufacture PVA based polymer films when, from Film making properties can be improved so as to suppress the thickness of film produce it is uneven and meanwhile when using metallic roll, band in film so that PVA systems Polymer film is from the viewpoint of these metallic rolls, the stripping taken become easily, the matching surface preferably in the film stoste Activating agent., can in the PVA based polymer films when manufacturing PVA based polymer films by the film stoste for being combined with surfactant Surfactant can be contained.The surfactant coordinated in film stoste for manufacturing PVA based polymer films and then PVA systems The species of the surfactant contained in polymer film is not particularly limited, and goes out from the viewpoint by metallic roll, the fissility taken Hair, preferably anionic surfactant or nonionic surfactant, particularly preferably nonionic surfactant.

As anionic surfactant, it is appropriate that the carboxylic acid type such as potassium laurate；The sulfuric acid such as octyl sulfate Ester type；Sulfonic acid types such as dodecyl benzene sulfonate etc..

As nonionic surfactant, it is appropriate that the alkyl ether type such as polyoxyethylene oleyl ether；Polyoxy second The alkyl phenyl ether type such as alkene octyl phenyl ether；The alkyl esters such as polyoxyethylene laurate；Polyoxyethylene laural base amino ethers etc. Alkyl amine type；The alkylamide type such as polyoxyethylene laural acid amides；The polypropylene glycol ether type such as polyoxyethylene poly-oxygen propylene aether；Laurate The alkylol amide types such as diglycollic amide, oleic acid diethyl amide；The allyl phenyl ether type such as polyoxy alkylidene allyl phenyl ether Deng.

These surfactants can be used alone or two or more is applied in combination.

In the film stoste for manufacturing PVA based polymer films during matching surface activating agent, the surface in film stoste The content of activating agent and then the content of the surfactant in PVA based polymer films are relative to film stoste or PVA based polymers The mass parts of PVA based polymers 100 included in film be preferably 0.01 ~ 0.5 mass parts in the range of, more preferably 0.02 ~ 0.3 matter In the range of amount part.By make the content of surfactant relative to the mass parts of PVA based polymers 100 be 0.01 mass parts with On, it is possible to increase Film making properties and fissility.On the other hand, by making the content of surfactant relative to PVA based polymers 100 Mass parts are below 0.5 mass parts, can suppress surfactant and ooze out into the surfaces of PVA based polymer films so as to glue Even, treatability reduces.

PVA based polymers film can only be made up of PVA based polymers or can be only by PVA based polymers and above-mentioned increasing Mould agent and/or surfactant to form, but as needed, can contain antioxidant, antifreezing agent, pH adjusting agent, screening agent, The other compositions in addition to above-mentioned PVA based polymers, plasticizer and surfactant such as anti-coloring agent, finish.

The containing ratio of PVA based polymers in PVA based polymer films be preferably 50 ~ 100 mass % in the range of, more preferably For in the range of 80 ~ 100 mass %, in the range of more preferably 85 ~ 100 mass %.

The thickness of PVA based polymer films is not particularly limited, preferably less than 60 μm, more preferably less than 50 μm, enter one Step is preferably less than 30 μm.On the other hand, due to can more successfully manufacture polarizing coating, the thickness is preferably more than 1 μm, more excellent Elect more than 3 μm as.

The shape of PVA based polymer films is not particularly limited, from can continuously manufacture polarizing coating with good productivity ratio Viewpoint is set out, preferably the film of strip.The length of the film of the strip is not particularly limited, can be according to manufactured polarizing coating Purposes etc. is suitably set, in the range of can reaching such as 5 ~ 20,000m.The width of the film of the strip is not particularly limited, can Think such as more than 50cm, the polarizing coating wide due to requiring width in recent years, therefore preferably more than 1m, more preferably 2m with Upper, more preferably more than 4m.The upper limit of the width of the film of the strip is not particularly limited, but if the width is wide, then When manufacturing polarizing coating by practical device, the tendency for being difficult to Uniform Tension be present, therefore the width of PVA based polymer films is excellent Elect below 7m as.

The form of PVA based polymer films is not particularly limited, and can be the form of individual layer, or can be for example in thermoplastic It is any by the form of layered product as the PVA based polymer films of the formation such as rubbing method on property resin film, but from stacking The viewpoints such as the cost of complicated property thermoplastic resin film of (coating etc.) operation are set out, preferably the form of individual layer.

The manufacture method of PVA based polymer films is not particularly limited, can preferentially using the thickness for making the film after film and Width becomes manufacture method evenly, for example, can use by form PVA based polymer films above-mentioned PVA based polymers, with And as needed further by one kind or two or more among plasticizer, surfactant and other compositions in liquid medium it is molten Stoste is film-made obtained from solution to manufacture；Using comprising PVA based polymers and as needed further comprising plasticizer, table The film stoste of one kind or two or more and PVA based polymers melting among face activating agent, other compositions and liquid medium is made Make.It is preferably that these compositions are equal when the film stoste contains at least one kind of among plasticizer, surfactant and other compositions Even mixing.

The aforesaid liquid medium used in preparation as film stoste, for example, water, dimethyl sulfoxide (DMSO), diformazan Base formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, ethylene glycol, glycerine, propane diols, diethylene glycol, triethylene glycol, Tetraethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamines etc., can be using one kind or two or more among these.This Among a little, from the burden to environment is small, from the viewpoint of recyclability, preferably water.

The volatilization fraction of stoste is film-made (by volatilizing, evaporating volatile ingredients such as the liquid mediums that is removed during film Content ratio in stoste is film-made), preferably 50 ~ 95 mass %s scope different according to film-forming method, film forming condition etc. In the range of interior, more preferably 55 ~ 90 mass %, in the range of more preferably 60 ~ 85 mass %.By making film stoste Volatilization fraction is more than 50 mass %, and the viscosity for being film-made stoste will not be too high, be successfully filmed stoste prepare when filtering, Deaeration so that the manufacture of the few PVA based polymer films of foreign matter, shortcoming becomes easy.On the other hand, by making waving for film stoste Hair fraction is below 95 mass %, and the concentration for being film-made stoste will not be too low so that the manufacture of industrial PVA based polymer films becomes Obtain easily.

As film-forming method when PVA based polymer films being filmed using above-mentioned film stoste, for example, Casting film method, extrusion film method, film by wet method, gel film method etc., preferably casting film method, extrusion film method.This A little film-forming methods be able to can also be combined using two or more only with a kind.Among these film-forming methods, from thickness can be obtained From the viewpoint of even width and the good PVA based polymer films of physical property, more preferably casting film method, extrusion film method. To PVA based polymer films, it can be dried, be heat-treated as needed.

, can be industrially preferably by for example following as the example of the specific manufacture method of PVA based polymer films Method：Machine mould etc. is applied using T-shaped slit die, hopper plate, I- moulds, lip, above-mentioned film stoste is sprayed or is cast in position In on the side face of the 1st heated roller (or band) of the rotation of most upstream side, from spraying or be cast to the 1st roller (or band) Side face on film side surface evaporation volatile ingredient so as to dry, then, be configured at 1 or more of side downstream It is further dried or is passed through on the side face of the heated roller of individual rotation in hot-air drying device so as to further After drying, batched by devices for taking-up.The drying carried out by heated roller and the drying carried out by hot-air drying device It can be implemented with appropriately combined.

By manufacture method as described above, can be readily derived substantial non-stretched (without stretch processing) PVA based polymer films.The PVA based polymers film can be directly Nian Jie with diaphragm using the bonding agent of the present invention, but this hair The PVA based polymer film Nian Jie with diaphragm is preferably the film of drawn, the particularly preferably light such as polarizing coating, phase retardation film in bright Learn film.

[manufacture method of polarizing coating]

Method when manufacturing polarizing coating using above-mentioned substantially non-stretched PVA based polymers film as initial film does not limit especially System, any means that use all the time can be used, for example, by implementing swelling treatment to PVA based polymers film, at dyeing Reason, stretch processing and further implementation crosslinking Treatment, fixing process, drying process, heat treatment etc. as needed, so as to Manufacture polarizing coating.Now, the order that swelling treatment, dyeing processing, stretch processing, fixing process etc. are respectively handled does not limit especially System, can also carry out the processing of 1 or more than 2 simultaneously.Further, it is also possible to carry out 2 times or each processing more than it in 1 Or more than 2.

Swelling treatment can be carried out by by PVA based polymer film immersions in water.The temperature for the water being impregnated in when in water In the range of preferably 20 ~ 40 DEG C of degree, in the range of more preferably 22 ~ 38 DEG C, in the range of more preferably 25 ~ 35 DEG C. In addition, as the time being impregnated in water, for example, in the range of preferably 0.1 ~ 5 minute, the scope of more preferably 0.5 ~ 3 minute It is interior.It should illustrate, be impregnated in water when in water and be not limited to pure water, can be the aqueous solution for having dissolved various composition, can also It is the mixture of water and aqueous medium.

Dyeing processing can use iodine system pigment to carry out, as the time point of dyeing, before being stretch processing, stretch processing When, after stretch processing in either phase.Dyeing is in general by making PVA based polymers film immersion in being used as containing for dye bath Have in the solution (the particularly aqueous solution) of iodine-potassium iodide to carry out, can also be compatibly using such dyeing side in the present invention Method.The concentration of iodine in dye bath be preferably 0.01 ~ 0.5 mass % in the range of, the concentration of KI be preferably 0.01 ~ 10 matter In the range of amount %.In addition, the temperature of dye bath is preferably 20 ~ 50 DEG C, particularly preferably 25 ~ 40 DEG C.

Crosslinking Treatment can be carried out by by PVA based polymer film immersions in the aqueous solution comprising crosslinking agent.If Crosslinking Treatment is carried out, then crosslinking is imported into PVA based polymer films, can effectively prevent from carrying out in higher temperature and with wet type The dissolution of PVA based polymers is into water during stretch processing.From such viewpoint etc., crosslinking Treatment is preferably after dyeing processing Carry out.As the crosslinking agent, can use one kind or two or more in the boron compounds such as the borates such as boric acid, borax.Crosslinking agent Concentration in the aqueous solution comprising crosslinking agent be preferably 1 ~ 15 mass % in the range of, in the range of more preferably 2 ~ 7 mass %. The aqueous solution comprising crosslinking agent can contain the auxiliary agents such as KI.The temperature of the aqueous solution comprising crosslinking agent is preferably 20 ~ 50 DEG C In the range of, more preferably in the range of 25 ~ 40 DEG C.

Stretch processing can be carried out by any one of wet tensile method or dry stretch process.The situation of wet tensile method In, it can carry out, can also be carried out in above-mentioned dye bath, in the bath of aftermentioned fixing process in the aqueous solution comprising boric acid.This Outside, in the case of dry stretch process, the PVA based polymers film after water suction can be used to carry out in atmosphere.Among these, preferably For wet tensile method, uniaxial tension is carried out more preferably in the aqueous solution comprising boric acid.Boric acid in boric acid aqueous solution it is dense Degree be preferably 0.5 ~ 6.0 mass % in the range of, more preferably in the range of 1.0 ~ 5.0 mass %, particularly preferably 1.5 ~ 4.0 matter In the range of amount %.In addition, boric acid aqueous solution can contain KI, its concentration is preferably in the range of 0.01 ~ 10 mass %.

Draft temperature in stretch processing is preferably in the range of 30 ~ 90 DEG C, in the range of more preferably 40 ~ 80 DEG C, it is special You Xuanwei not be in the range of 50 ~ 70 DEG C.

In addition, the stretching ratio in stretch processing is from the viewpoint of the polarization property of gained polarizing coating, preferably 5 times with Above, more preferably more than 5.5 times, particularly preferably more than 6 times.The upper limit of stretching ratio is not particularly limited, and stretching ratio is excellent Elect less than 8 times as.

When manufacturing polarizing coating, in order that absorption of the dyestuff (iodine etc.) to PVA based polymer films becomes strong, preferably consolidated Fixed processing.As the fixing process bath used in fixing process, can use comprising boron such as one kind or two or more boric acid, boraxs The aqueous solution of compound.In addition, as needed, iodine compound, metallic compound are added in being bathed to fixing process.Bearing In general the concentration of boron compound in reason bath is preferably 2 ~ 15 mass %, particularly preferably 3 ~ 10 mass % or so.Bearing The temperature of reason bath is preferably 15 ~ 60 DEG C, particularly preferably 25 ~ 40 DEG C.

Drying process is preferably carried out at 30 ~ 150 DEG C, is especially more preferably carried out at 50 ~ 130 DEG C.By above-mentioned At a temperature in the range of dry, be readily obtained the polarizing coating of excellent in dimensional stability.

[other PVA based polymers films]

Among the bonding agent of the present invention PVA based polymer film Nian Jie with diaphragm, as except above-mentioned polarizing coating and phase PVA based polymer films outside potential difference film, for example, the optical film in addition to polarizing coating and phase retardation film, conduction It is film, photosensitive film, diaphragm, stripping film, rust-preventing film, cover layer, transfer film, grinding film, window film, decorating film, adhesive film, anti- Shake steel plate film, raw decomposability film, antibacterial film etc..As the optical film in addition to polarizing coating and phase retardation film, can enumerate Such as antireflection film, alignment films, polarization layer diaphragm, angle of visibility improve film, brightness improves film, electromagnetic shielding film, photomask, red Outside line screened film, ultraviolet screener film, filter, optical low-pass filter (OLPF) film, weatherable films etc..

[diaphragm]

It is not particularly limited using the bonding agent of the present invention diaphragm Nian Jie with PVA based polymer films, for example, bag Containing ionomer, polyethylene, cellulose, tri acetyl cellulose (TAC), (methyl) acrylic acid series polymeric compounds, structure containing ester ring type Polymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, makrolon, polystyrene, polypropylene The polymer such as nitrile, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer, nylon Film.Among these, when using polarizing coating or phase retardation film as PVA based polymers film, from good conduct can be played The viewpoints such as the function of diaphragm are set out, preferably the film comprising tri acetyl cellulose, include (methyl) acrylic acid series polymeric compounds Film, the film of the film comprising polyester or the polymer comprising the structure containing ester ring type.As containing for the above-mentioned polymer in above-mentioned film There is rate, preferably more than 50 mass %, be more preferably more than 80 mass %, more preferably more than 85 mass %.

In addition, in order to further improve the bonding force of said protection film and bond layer, as needed, can also be to above-mentioned The surface of diaphragm is modified by known sided corona treatment, corona treatment, UV processing, flame treatment etc..

The thickness of said protection film is not particularly limited, preferably less than 200 μm, more preferably less than 100 μm.The opposing party Face, from the viewpoint of the mechanical strength for improving gained convered structure, the thickness is preferably more than 5 μm, more preferably more than 10 μm.

[purposes of bonding agent]

As the purposes of the bonding agent of the present invention, can enumerate as described above makes polarizing coating or phase retardation film Nian Jie with diaphragm Purposes (polarization plates or the manufacture purposes of polarizer)；Make synthetic resin in the manufacture of electronic component, electronic equipment etc., rubber Purposes Nian Jie with PVA based polymer films such as glue etc., in the manufacture of polarization plates or the manufacture purposes of polarizer, wherein polarization plates It is particularly useful in purposes.

The bonding agent of the present invention shows high bonding force in PVA based polymers film is bonding with diaphragm.The bonding agent The bonding force of PVA based polymers film and diaphragm after solidification be preferably more than 6.0N/25mm, more preferably 6.5N/25mm with Upper, more preferably more than 7.0N/25mm.It should illustrate, the peeling force can be obtained by method described later in embodiment.

＜ convered structures ＞

Then, illustrated for the embodiment of the convered structure of the present invention.Fig. 1 convered structure 1 possess PVA based polymers film 2, Diaphragm 4 and the bond layer 3 being disposed between above-mentioned PVA based polymers film 2 and diaphragm 4.Here, bond layer 3 is by this The bonding agent of invention is formed.

[bond layer]

Bond layer 3 is formed by the bonding agent.Specifically, can be by irradiating active energy beam to the bonding agent and shape Into.Bond layer 3 can contain additive according to the purposes of convered structure 1.

The thickness of bond layer 3 is not particularly limited, but if excessively thin, then PVA based polymers film 2 and diaphragm 4 be present The tendency that reduces of bonding force, if in addition, blocked up, the tendency for the thickness for unnecessarily increasing convered structure 1 be present, therefore viscous The thickness for connecing oxidant layer 3 is preferably more than 0.1 μm, more preferably more than 0.2 μm, is more preferably more than 0.3 μm, particularly preferably For more than 0.5 μm, furthermore it is preferred that being less than 500 μm, more preferably less than 50 μm, more preferably less than 20 μm, especially excellent Elect less than 10 μm as.

The manufacture method ＞ of ＜ convered structures

Convered structure 1 can be manufactured by possessing the manufacture method of following step：By PVA based polymers film 2 and diaphragm 4 by The step of bonding agent fitting of the present invention (laminating step) and active energy beam is irradiated after the laminating step so that viscous The step of connecing agent solidification (irradiating step).

[laminating step]

In laminating step, PVA based polymers film 2 is bonded with diaphragm 4 by the bonding agent of the present invention.The applying method does not have Especially limitation, from the viewpoint of it can more easily be bonded, preferably in the surface of PVA based polymer films and diaphragm Surface one or both of after the bonding agent of the upper coating present invention, the side that overlaps the PVA based polymers film and diaphragm Method.The surface of PVA based polymer films and the surface of diaphragm one or both of on be coated with the bonding agent of the present invention when Coating method be not particularly limited, for example, die coating method, rolling method, air knife rubbing method, gravure roller coating method, scrape roller The methods of coating, scraper for coating method, curtain flow coat method, spray-on process, silk rod method, stick coating method, dipping, brushing.

In addition, as applying method, in addition to that mentioned above, can also use makes PVA based polymer films be overlapped with diaphragm Afterwards, the method for the bonding agent of the present invention is impregnated with therebetween.

Further, in laminating step, gained layered product can be pressurizeed by roller etc..Now, the material as above-mentioned roller Matter, for example, metal, rubber etc..The roller of PVA based polymer films side can be identical material with the roller of diaphragm side, It can be unlike material.

[irradiating step]

By irradiating active energy beam to the above-mentioned layered product after fitting so that uncured bonding agent solidifies, can obtain The convered structure of the present invention., can be according to the species of the various composition included in bonding agent of the invention as active energy beam Appropriate selection.As active energy beam, as set forth above, it is possible to enumerate the electricity such as ultraviolet, infrared ray, X ray, gamma-rays Magnetic wave, electron ray in addition, proton radiation, neutron ray etc., from curing rate, the availability of irradiation unit, price Set out etc. viewpoint, preferably ultraviolet or electron ray, more preferably ultraviolet.

Above-mentioned active energy beam can use known device to irradiate.During using ultraviolet as active energy beam, High-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, carbon arc lamp, the metal halogen of the light for the wavelength region for launching below 450nm can be used Compound lamp, xenon lamp, chemical lamp, LED etc..In addition, during using electron ray (EB) as active energy beam, as accelerating electricity Pressure, in the range of preferably 0.1 ~ 10MeV, as illuminated line amount, in the range of preferably 1 ~ 500kGy.

The accumulated light of above-mentioned active energy beam is not particularly limited, preferably 10 ~ 20,000mJ/cm²In the range of, More preferably 30 ~ 5,000mJ/cm²In the range of.If the accumulated light of active energy beam is very few, deposit after hardening The tendency that the bonding force of PVA based polymers film and diaphragm reduces.On the other hand, if the accumulated light mistake of active energy beam More, then convered structure produces superfluous heat, bond layer, the tendency of PVA based polymers film deterioration be present.

In the irradiation process of active energy beam or after irradiation, consolidating for bonding agent can be promoted as desired by heating Change.As the heating-up temperature, in the range of the viewpoint such as influence to curing rate, each layer, preferably 40 ~ 130 DEG C, more In the range of preferably 50 ~ 100 DEG C.

By the solidification of the bonding agent of the present invention, bond layer is formed, the convered structure of the present invention can be obtained.

＜ other embodiments ＞

The convered structure of the present invention can have multiple bond layers.For example, in PVA based polymer films, can with it is as described above Ground, which is formd on the opposite side in bond layer side, also has bond layer and in the PVA based polymers with bond layer Another diaphragm etc. is laminated in film opposite side, so that with diaphragm/bond layer/PVA based polymers film/bond layer/ The structure of diaphragm.

When the convered structure of the present invention is polarization plates, after the adhesives such as acrylic acid series can be coated with the polarization plates, fitting In on glass substrate, so as to the part as LCD.Meanwhile film, brightness raising film etc. can be improved with phase retardation film, angle of visibility Fitting.

Embodiment

The present invention is further illustrated by following embodiments, but the present invention is not because of these embodiments and by any limit It is fixed.It should illustrate, each evaluation used in following embodiments and comparative example or assay method are shown in hereafter.

The evaluation of bonding force

The polarization plates obtained in following each embodiments or comparative example are further statically placed in 24 in 23 DEG C of temperature, relative humidity 50% After hour, to each embodiment or comparative example, alongst (draw direction of polarizing coating) is cut out respectively from the polarization plates The diaphragm of 5 250mm × width 25mm short strip shape.Then, to each diaphragm, respectively in the poly- methyl of polarizing coating and side Between methyl acrylate film, according to based on JIS K 6854-3：1999 T mould disbonded tests are peeled off, and gained is peeled off The average value of power (5 times) is denoted as bonding force.In the experiment, condition determination is that peeling rate is 30mm/ minutes.It should illustrate, two Bonding force between film is too high so that when polymethyl methacrylate film is destroyed, is evaluated as " material damage ".

The evaluation of water resistance

The polarization plates obtained in following each embodiments or comparative example are impregnated 48 hours in 60 DEG C of water.Thereafter, by polarization plates Lift from water, stripping is whether there is between polarizing coating and polymethyl methacrylate film according to the evaluation of following determinating references.

A：Without stripping

B：There is stripping.

The assay method of water contact angle

The diaphragm of 50mm square is cut out from the polymethyl methacrylate film as measure object, based on JIS R 3257： The water that 1999 (base plate glass wettability of the surface test method) measure is contacted with the bonding agent of the diaphragm on the surface of side connects Feeler.That is, the water droplet below 4 μ l is stood on horizontal positioned diaphragm, according to the shape of water droplet, determines and is connect with the diaphragm of water droplet The radius r (mm) and membrane surface on tactile surface obtain water contact angle to the height h (mm) on water droplet summit by following formula (1) θ(°)。

θ = 2tan^-1(h/r) (1)。

It should illustrate, measure is implemented 5 times, is averaged the water contact angle that value is denoted as the film.In addition, measure is in temperature：25 DEG C, humidity：Carried out under conditions of 50%RH.

[embodiment 1 ~ 4 and comparative example 1 ~ 5]

The manufacture ＞ of ＜ bonding agents

To the container with agitating device that can be closed, each material is put into the mixing ratio shown in table 1, stirred by 24 hours Mix and uniformly mix, so as to obtain bonding agent.It should illustrate, the content of each material is as described below.

《PVA based polymers (A)》

PVA：Saponified (the saponification degree of the homopolymer of vinyl acetate：40 moles of %, by containing for the vinyl alcohol units of acetalation Rate：0 mole of %, the degree of polymerization：250).

PVB：By the saponified polyvinyl butyral resin (second obtained from n-butanal acetalation of the homopolymer of vinyl acetate The containing ratio of alcohol units：28 moles of %, by the containing ratio of the vinyl alcohol units of acetalation：70 moles of %, vinyl ester units Containing ratio：2 moles of %, the degree of polymerization：500).

《Polyalcohol》

PO-1：PEPA (Co., Ltd.'s Network ラレ systems " Network ラレ Port リオー Le P-5010 ")

PO-2：Polycarbonate polyol (Co., Ltd.'s Network ラレ systems " Network ラレ Port リオー Le C-2090 ").

《Cationically polymerizable compound (B)》(except aftermentioned with cationically polymerizable and with free-radical polymerised Outside compound (BD))

B-1：3- ethyl -3- hydroxymethyl oxetanes (Toagosei Co., Ltd's system " OXT-101 ")

B-2：3', 4'- epoxycyclohexyl-methyl 3,4- epoxycyclohexane carboxylates (Co., Ltd. ダイセ Le systems " セロキサイド2021P”)。

《Cationic polymerization initiators (C)》

C-1：The mass % solution of propylene carbonate 50 (the サ Application アプロ of diphenyl [4- (thiophenyl) phenyl] sulfonium hexafluorophosphate Co. Ltd. system " CPI-100P ").

《Free-radical polymerised compound (D)》

D-1：Benzyl acrylate (Osaka Organic Chemical Industry Co., Ltd.'s system " PVC スコート 160 ")

D-2：Three (2- hydroxyethyls) isocyanurate triacrylates (Toagosei Co., Ltd's system " アロニッ Network ス M- 315”)。

《Radical polymerization initiator (E)》

E-1：1- hydroxycyclohexylphenylketones (BASF systems " IRGACURE 184 ").

《With cationically polymerizable and with free-radical polymerised compound (BD)》

BD-1：3- ethyl -3- acryloyloxymethyls oxetanes (Osaka Organic Chemical Industry Co., Ltd. system " OXE- 10”)。

The manufacture ＞ of ＜ convered structures (polarization plates)

As diaphragm, polymethyl methacrylate film (Co., Ltd. that thickness is 50 μm, size is 300mm × 100mm is used Network ラレ systems), on the surface of the side of the polymethyl methacrylate film, above-mentioned bonding agent is coated with using bar coater.Then, By the bonding agent, thickness is set (to polymerize for the polarizing coating of 80mm on 280mm × width on 10 μm, draw direction to PVA systems Thing film is implemented by the dyeing and uniaxial tension of the progress of iodine system pigment the film that manufactures) coincide with said protection film.Thereafter, exist Above-mentioned polarizing coating is not contacted on the surface of side with bonding agent, using bar coater, is coated with bonding agent same as described above, as Another diaphragm, use polymethyl methacrylate film (Co., Ltd. Network ラ that thickness is 50 μm, size is 300mm × 100mm レ systems), overlapped by the bonding agent with above-mentioned polarizing coating.There is polymethyl methacrylate by what is obtained in this way The layered product that the layer of film/bonding agent/polarizing coating/bonding agent/polymethyl methacrylate film is formed by laminating machine so as to extrude, To cause the thickness of the part of bonding agent to respectively reach 1 μm.

Thereafter, it is right using ultraviolet lamp (as lamp, using the metal halide lamp of GS YUASA Co., Ltd.) Above-mentioned layered product reaches 700mJ/cm with accumulated light²Mode irradiate ultraviolet.It should illustrate, for the accumulated light, make Determined with UV measuring appliances (GS YUASA Co., Ltd.).After irradiating ultraviolet, in 50% time 23 DEG C of temperature, relative humidity standing 24 hours, so as to obtain the polarization plates as convered structure.It should illustrate, for each embodiment or comparative example, respectively in order to evaluate Bonding force and manufacture 2 polarization plates, 1 polarization plates is manufactured to evaluate water resistance.In addition, in embodiment 3 and 4, for each From polarization plates manufacture in 2 polymethyl methacrylate films using, 2 using the table that side pair is contacted with bonding agent Face implements the polymethyl methacrylate film of sided corona treatment.

＜ evaluates ＞

For above-mentioned polarization plates, the evaluation of bonding force and water resistance is carried out by the above method.As a result it is shown in table 1.

[table 1]

。

Description of reference numerals

1 convered structure

2 PVA based polymer films

3 bond layers

4 diaphragms.

Claims

1. the bonding agent of active energy ray curable, it is for being bonded the film and diaphragm that include vinol series polymer Bonding agent, it includes vinol series polymer (A), cationically polymerizable compound (B) and cationic polymerization initiators (C)。

2. bonding agent according to claim 1, it also triggers comprising free-radical polymerised compound (D) and radical polymerization Agent (E).

3. bonding agent according to claim 1 or 2, wherein, at least a portion in cationically polymerizable compound (B) is With cationically polymerizable and with free-radical polymerised compound (BD).

4. the bonding agent according to any one of claim 1 ~ 3, wherein, vinol series polymer (A) is by acetalation Vinyl alcohol units containing ratio less than the polyvinyl alcohol that 10 moles of % and saponification degree are 80 moles of below %.

5. the bonding agent according to any one of claim 1 ~ 3, wherein, vinol series polymer (A) is by acetalation Vinyl alcohol units containing ratio for 10 moles of more than % Pioloform, polyvinyl acetal.

6. bonding agent according to claim 5, wherein, Pioloform, polyvinyl acetal is polyvinyl butyral resin.

7. the bonding agent according to any one of claim 1 ~ 6, wherein, the containing ratio of vinol series polymer (A) is 1 ~ 90 mass %.

8. convered structure, it is to possess：The convered structure of film, diaphragm and bond layer comprising vinol series polymer, its In, bond layer is equipped between the film and diaphragm comprising vinol series polymer, and bond layer is by claim 1 Bonding agent any one of ~ 7 solidifies and obtained.

9. convered structure according to claim 8 is comprising the film of vinol series polymer is the film of drawn.

10. convered structure according to claim 8 or claim 9, wherein, the film of above-mentioned drawn is polarizing coating or phase retardation film.

11. the convered structure according to any one of claim 8 ~ 10, wherein, diaphragm includes tri acetyl cellulose, (first Base) acrylic acid series polymeric compounds, polyester or the structure containing ester ring type polymer.

12. the convered structure according to any one of claim 8 ~ 11 is comprising film and the guarantor of vinol series polymer The bonding force of cuticula is more than 6.0N/25mm.

13. the manufacture method of convered structure, the film comprising vinol series polymer and diaphragm are appointed by claim 1 ~ 7 After bonding agent fitting described in one, irradiation active energy beam is so that bond layer solidifies.